CN113667375B - 一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体及其复合材料以及制备方法 - Google Patents

一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体及其复合材料以及制备方法 Download PDF

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CN113667375B
CN113667375B CN202110876124.6A CN202110876124A CN113667375B CN 113667375 B CN113667375 B CN 113667375B CN 202110876124 A CN202110876124 A CN 202110876124A CN 113667375 B CN113667375 B CN 113667375B
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CN113667375A (zh
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吴晓宏
李杨
崔凯
秦伟
卢松涛
洪杨
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Harbin Institute of Technology
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Abstract

一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体及其复合材料以及制备方法；属于辐照屏蔽材料制备及其应用领域。本发明解决传统稀土金属氧化物受到辐照易产生二次辐射、易在有机树脂基体中团聚、浸润性差、对中子屏蔽性能差等缺点，与树脂基底形成复合涂层材料时强度差等缺点。本发明的纳米粉体材料呈核壳结构；稀土金属氧化物纳米颗粒为核，低Z金属氧化物包覆层为壳，由稀土金属氧化物纳米颗粒外表面均匀沉积低Z金属氧化物薄膜组成。将其与树脂混合，均匀的分散到有机树脂基体中，形成涂层或者块状结构。本发明可提高航天器集成电路封装的可靠性，免受γ射线、中子辐射的影响，还可应用于核辐射防护、医学X射线防护等领域。

Description

一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体及其复合 材料以及制备方法
技术领域
本发明属于辐照屏蔽材料制备及其应用领域。
背景技术
空间环境中存在不同水平的辐射，航天器的电子器件以及芯片暴露于超出集成电路芯片总耐受剂量辐射下，导致电子器件和芯片性能受到影响，甚至使得电子器件及其集成电路无法工作。稀土氧化物纳米颗粒复合涂层作为一种新型的辐射屏蔽材料，在一定范围内能够有效吸收辐射粒子，将电子器件及芯片受到的空间辐射降低至总耐受剂量辐射之下。
近年来，由于稀土纳米颗粒对γ射线的屏蔽效果比硼等低Z元素明显，此外，稀土元素原子结构特殊，具有弥补铅的＂弱吸收区＂的优势、而且其对热中子的n、γ反应截面的面积高出硼几十倍，与慢中子和中能中子的反应截面同样比硼高数倍。众多优势使稀土防辐射材料设计和制备成为防辐射材料的研究重点。但稀土纳米颗粒存在一定的二次放射性(与β粒子产生轫致辐射、与中子易产生γ辐射)，且在与树脂基底成膜时的易团聚，浸润性差等缺点，因此需要对稀土纳米颗粒进行改性。
发明内容
本发明旨在解决传统稀土金属氧化物受到辐照易产生二次辐射、易在有机树脂基体中团聚、浸润性差、对中子屏蔽性能差等缺点，与树脂基底形成复合涂层材料时强度差等缺点，提供了一种高度可控、在有机树脂基体中分散性好、浸润性强、能增强有机树脂基体强度、有效降低二次辐射，且提高了对X、γ辐射屏蔽性能、增强了对中子屏蔽能力的改性稀土氧化物纳米颗粒粉体。成形后的粉体材料与有机树脂基体混合，均匀分散在有机树脂中可形成涂层、块状结构。
本发明提供了一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体呈核壳结构；稀土金属氧化物纳米颗粒为核，低Z金属氧化物包覆层为壳，由稀土金属氧化物纳米颗粒外表面均匀沉积低Z金属氧化物薄膜组成。将其与树脂混合，均匀的分散到有机树脂基体中，形成涂层或者块状结构。图1为本发明制得的涂层结构示意图。
进一步地限定，所述低Z金属氧化物包覆层选自TiO2、Al2O3、ZnO中的任意一种或至少两种的组合，优选ZnO。采用ZnO可以更有效降低稀土金属氧化物收到辐射时产生的二次辐射粒子，且能更好的降低粉体团聚，增强稀土金属氧化物在有机树脂基体中的浸润性和有机树脂基体的强度。
进一步地限定，所属有机树脂基体选自氰酸酯、环氧树脂、聚氨酯或高含氢聚乙烯等。
在本发明中屏蔽中子和γ射线的纳米稀土氧化物复合粉体是采用原子层沉积法制备的；具体是按下述步骤进行的：
步骤一、稀土金属氧化物纳米颗粒转移至原子层沉积装置腔体内；
步骤二、通入氧源进行沉积，沉积完成后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤三、再通入反应前驱体沉积低Z金属氧化物，然后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤四、重复步骤二至三的操作；即得到所述纳米稀土氧化物复合粉体。
进一步地限定，步骤二中以高纯度水、去离子水或者臭氧作为氧源，在0.10-0.20torr真空环境中，反应温度为150℃-200℃，脉冲时间为0.02s，反应时间为6S。
进一步地限定，步骤三中以二乙基锌、三甲基铝、四异丙醇钛中的一种或者多种作为反应前驱体，在0.10-0.20torr真空环境中，反应温度为150℃-200℃，脉冲时间为0.02s，反应时间为6S。
反应温度可以控制在150℃、160℃、170℃、180℃、190℃、200℃。
清洗气体必须是不与稀土金属氧化物纳米颗粒和反应前驱体相互反应的气体物质；本反应采用的清洗气体可采用高纯度的氮气(99.999％)。
本发明可以通过重复步骤二至三的次数来控制稀土金属氧化物纳米颗粒外包覆的低Z金属氧化物厚度。所述的低Z金属氧化物包覆层平均厚度为6-50nm。优选地，低Z金属氧化物包覆层的厚度为6nm-30nm，例如6nm、9nm、20nm、25nm、40nm、50nm等。
进一步限定，重复步骤二至三的操作29次-299次，重复操作次数可为49次、99次、149次、199次、249次等。
本发明中屏蔽中子和γ射线的复合材料的制备方法包括以下步骤：
步骤(A)将屏蔽中子和γ射线的稀土金属氧化物改性的纳米稀土氧化物复合粉体与有机树脂基体混合，在三锟研磨机上搅拌5min-10min；
步骤(B)然后通过刮涂、旋涂或喷涂在基体上，或者制备成块状材料。
步骤(C)然后在真空干燥箱中以温度为30℃-80℃干燥3小时-8小时，干燥温度可以控制在30℃、40℃、50℃、60℃、70℃、80℃，干燥时间可以控制在3、4、5、6、7、8小时。
进一步地，所述的纳米稀土氧化物复合粉体的质量分数为10％～70％，优选为20％、30％、40％、50％、60％。
本发明利用低Z材料包覆改性纳米颗粒，核壳纳米颗粒之间组成微观多层叠加结构，可以有效降低稀土纳米颗粒的二次放射性，提高稀土纳米颗粒在树脂中的浸润性，有效降低稀土纳米颗粒的团聚，核壳纳米填料还能提高稀土氧化物颗粒对辐射的屏蔽性能，核壳纳米填料还对树脂基体起到增强作用，并且在稀土金属氧化物纳米颗粒粉末中加入低Z金属氧化物能提高该材料对中子的吸收能力。
本发明方法可以有效控制包覆改性膜的厚度；包覆在稀土氧化物纳米颗粒的薄膜致密均匀；在稀土氧化物纳米颗粒表面形成的低Z包覆层纯度高，无其他杂质；在纳米粉体表面进行原位气相生长，可以有效避免粉体的团聚现象；可通过改变沉积速度、沉积循环数、沉积温度等工艺条件该表沉积物的比例和用量。
本发明通过ALD工艺在稀土氧化物纳米颗粒沉积一层致密且厚度可控的低Z金属氧化物，有利于该涂层对中子的吸收与屏蔽；
本发明核壳纳米颗粒之间可组成微观多层叠加结构，可有效屏蔽中子和γ辐照，且有效屏蔽和减少二次粒子；
本发明的核壳纳米填料对树脂基体起到增强作用。
本发明提高航天器集成电路封装的可靠性，免受γ辐射、中子辐射的影响，此材料还可应用于核辐射防护、医学X射线防护等。
附图说明
图1是本发明制得的涂层结构示意图；
图2是氧化钆改性前后的线性衰减系数图；
图3是结合力测试前照片；
图4是结合力测试后照片。
具体实施方式
实施例1：将纳米氧化钆转移至原子层沉积装置腔体内，对纳米氧化钆进行低Z金属氧化物包覆改性；具体是按下述步骤进行的：反应温度应控制在150℃，反应过程中压力应该控制在0.15torr，以高纯度水作为氧源，脉冲时间为0.02s，反应时间为6S，脉冲反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s；低Z金属氧化物源为二乙基锌，脉冲时间为0.02s，反应时间为6s，脉冲、反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s。然后氧源与低Z金属氧化物源交替通入反应腔体内作为一个循环周期。一共循环50次即可得到纳米稀土氧化物复合粉体。
纳米稀土氧化物复合粉体与环氧树脂混合，其中粉体质量分数为50％，环氧树脂质量分数为50％。将混合后的粉体与树脂倒入三锟研磨机中，研磨搅拌10min。然后将搅拌均匀的浆液采用刮涂的方式刮涂在聚酰亚胺薄膜上。再在真空干燥箱中以30℃干燥3h即可得到薄膜材料。
实施例2：将纳米氧化钆转移至原子层沉积装置腔体内，对纳米氧化钆进行低Z金属氧化物包覆改性；具体是按下述步骤进行的：反应温度应控制在150℃，反应过程中压力应该控制在0.15torr，以高纯度水作为氧源，脉冲时间为0.02s，反应时间为6S，脉冲反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s；低Z金属氧化物源为二乙基锌，脉冲时间为0.02s，反应时间为6s，脉冲、反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s。然后氧源与低Z金属氧化物源交替通入反应腔体内作为一个循环周期。一共循环150次即可得到纳米稀土氧化物复合粉体。
纳米稀土氧化物复合粉体与环氧树脂混合，其中粉体质量分数为50％，环氧树脂质量分数为50％。将混合后的粉体与树脂倒入三锟研磨机中，研磨搅拌10min。然后将搅拌均匀的浆液采用刮涂的方式刮涂在聚酰亚胺薄膜上。再在真空干燥箱中以30℃干燥3h即可得到薄膜材料。
实施例3：将纳米氧化钆转移至原子层沉积装置腔体内，对纳米氧化钆进行低Z金属氧化物包覆改性；具体是按下述步骤进行的：反应温度应控制在150℃，反应过程中压力应该控制在0.15torr，以高纯度水作为氧源，脉冲时间为0.02s，反应时间为6S，脉冲反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s；低Z金属氧化物源为二乙基锌，脉冲时间为0.02s，反应时间为6s，脉冲、反应完成后用高纯氮气(99.999％)吹扫管路和腔体内的残余反应物和副产物40s。然后氧源与低Z金属氧化物源交替通入反应腔体内作为一个循环周期。一共循环300次即可得到纳米稀土氧化物复合粉体。
纳米稀土氧化物复合粉体与环氧树脂混合，其中粉体质量分数为50％，环氧树脂质量分数为50％。将混合后的粉体与树脂倒入三锟研磨机中，研磨搅拌10min。然后将搅拌均匀的浆液采用刮涂的方式刮涂在聚酰亚胺薄膜上。再在真空干燥箱中以30℃干燥3h即可得到薄膜材料。
本发明通过线性衰减系数来评判抗辐照能力，单一能量的γ射线或X射线在目标材料的线性衰减如下：
I＝I0exp(-μx)
I和I0分别是投射光强度和入射光强度，x是材料的厚度，μ是线性衰减系数。对于γ射线来说，μ是γ射线穿过屏蔽材料的线性衰减系数,它表明屏蔽材料对于γ射线总的吸收系数，相当于材料对γ射线的宏观吸收截面，μ的量纲为长度的倒数，显然μ直接指出了材料对于γ射线的屏蔽能力。μ越大说明该材料对于伽马射线吸收越强，衰减伽马射线地能力越强。
从图2可以看出未被低Z金属氧化物未包覆改性地氧化钆线性衰减系数未5.348，而被低Z金属氧化物未包覆改性地氧化钆线性衰减系数均大于5.348。说明了包覆改性后地氧化钆吸收伽马射线地能力明显优于未包覆改性地氧化钆。且半包覆(50cy)时线性衰减系数高达6.609，优于全包覆(150cy、300cy)。
本发明通过画格法来评判涂层的结合力。参考ISO 2409标准，该实验膜厚度为170um，故间隔3mm用单刃刀具划线。然后用胶带粘，抓着胶带一头，在0.5-1.0s内，以接近60°角撕开胶带。检查切割部位的状态，如图3和图4所示。参考ISO 12944-6中规定，达到0级或1级为合格。参考标准说明制备的涂层与聚酰亚胺基体结合力为1级，结合力合格。

Claims (10)

1.一种屏蔽中子和γ射线的纳米稀土氧化物复合粉体，其特征在于所述纳米稀土氧化物复合粉体呈核壳结构；稀土金属氧化物纳米颗粒为核，低Z金属氧化物包覆层为壳；
其中，所述纳米稀土氧化物复合粉体的制备方法是采用原子层沉积法制备的；具体是按下述步骤进行的：
步骤一、稀土金属氧化物纳米颗粒转移至原子层沉积装置腔体内；
步骤二、通入氧源进行沉积，沉积完成后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤三、再通入反应前驱体沉积低Z金属氧化物，然后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤四、重复步骤二至三的操作；即得到所述纳米稀土氧化物复合粉体。
2.根据权利要求1所述的纳米稀土氧化物复合粉体，其特征在于所述低Z金属氧化物包覆层是由TiO2、Al2O3、ZnO中的任意一种或至少两种的任意比组合。
3.根据权利要求1所述的纳米稀土氧化物复合粉体，其特征在于低Z金属氧化物包覆层平均厚度为6nm-50nm。
4.如权利要求1、2或3所述的纳米稀土氧化物复合粉体的制备方法，其特征在于所述制备方法是采用原子层沉积法制备的；具体是按下述步骤进行的：
步骤一、稀土金属氧化物纳米颗粒转移至原子层沉积装置腔体内；
步骤二、通入氧源进行沉积，沉积完成后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤三、再通入反应前驱体沉积低Z金属氧化物，然后用清洗气体吹扫管路和腔体内的残余反应物和副产物；
步骤四、重复步骤二至三的操作；即得到所述纳米稀土氧化物复合粉体。
5.根据权利要求4所述的制备方法，其特征在于步骤二中以高纯度水、去离子水或者臭氧作为氧源，在0.10-0.20torr真空环境中，反应温度为150℃-200℃，脉冲时间为0.02s，反应时间为6s；步骤三中以二乙基锌、三甲基铝、四异丙醇钛中的一种或者多种作为前驱体，在0.10torr-0.20torr真空环境中，反应温度为150℃-200℃，脉冲时间为0.02s，反应时间为6s。
6.根据权利要求4所述的制备方法，其特征在于重复步骤二至三的操作29次-299次。
7.屏蔽中子和γ射线的复合材料，其特征在于所述复合材料是将权利要求1-3任意一项所述的纳米稀土氧化物复合粉体或者权利要求4-6任意一项所述方法制备的纳米稀土氧化物复合粉体均匀分散到有机树脂基体中，形成涂层或者块状结构。
8.根据权利要求7所述的复合材料，其特征在于有机树脂基体为氰酸酯、环氧树脂、聚氨酯、高含氢聚乙烯中的一种。
9.根据权利要求7所述的复合材料，其特征在于所述的纳米稀土氧化物复合粉体的质量分数为10％～70％。
10.如权利要求7、8或9所述复合材料的制备方法，其特征在于：
步骤(A)将屏蔽中子和γ射线的纳米稀土氧化物复合粉体与有机树脂基体混合，在三锟研磨机上搅拌5-10min；
步骤(B)然后通过刮涂、旋涂或喷涂在基体上，或者制备成块状材料；
步骤(C)然后在真空干燥箱中以温度为30℃-80℃干燥3-8小时。
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